Fabrication of Free Standing Membranes and Use Thereof for Synthesis of Nanoparticle Patterns

ABSTRACT

The present disclosure discloses a method of fabrication of free standing open pore membranes with uniform pore size and shape and ordered pore distribution, and its use for synthesis of nanoparticle patterns. The method includes applying a photoresist layer to the top surface of a substrate, heating the photoresist layer for a period of time, and exposing the photoresist layer to a dose of ultraviolet radiation through a mask having a predetermined pattern. The dose of ultraviolet radiation is controlled in intensity and time and the photoresist layer is exposed such that a top portion of the photoresist layer through which the dose of ultraviolet radiation enters the photoresist layer undergoes greater cross linking than a bottom portion of the photoresist layer immediately adjacent to the top surface of the substrate such that a cross linking gradient develops through a thickness of the photoresist layer. The mask is removed and the membrane is readily detached from the top surface of the substrate since the portion of the membrane adjacent to the top surface is less cross linked than the top surface of the membrane. The detached membrane forms a free standing patterned membrane having a preselected pattern of open pores. The method can be used with positive photoresist materials as well when deposited on a UV transparent substrate so that the photoresist can be exposed to UV from its top with photomask and UV exposure from its back of the transparent substrate without the photomask.

FIELD

The present invention relates to a method of fabrication of freestanding membranes with open pore structures and synthesis ofnanoparticle patterns using these membranes.

BACKGROUND

Membrane with uniform pore size and shape, and ordered pore distributionare very desirable because of their superior performance compared toconventional membranes in many applications such as filtration, templatesynthesis, and catalytic reaction. These characteristics of membraneshave not yet been satisfactorily achieved by existing membranefabrication methods including bombardment and wet etching fortrack-etched membranes, electrochemical etching for anodic aluminamembranes, replication of polymer membranes from molding templates,dissolution of embedded particles to yield porous membranes, and thedirect photolithographic method. The photolithographic method canpattern photoresist membranes with well-defined and ordered pores onsubstrates, which is the nature of photolithography. However, inprevious photolithographic methods, the membranes cannot be easilydetached from substrates, so that additional sacrificial layers arerequired. Not only are the cost and complexity of the fabricationprocess increased, but the quality of membranes produced this way isimpaired as well when the sacrificial layer is dissolved either incorrosive solution, or by lateral isotropic etching.

Commercially available track-etch membranes (Nuclepore, Poretics,Osmonics and Millipore), prepared by bombardment and wet etching sufferfrom difficultly to have good control over the morphology and pore sizeof the pores. Except for the expensive photolithographic methodmentioned above, typically porous membranes made using known methodssuffer from a poor coefficient of variation (CV), meaning a widevariation in pore size in all direction, slanted walls through thethickness of the membrane, variation in pore diameter from one pore tothe other etc., such that these membranes with poor CV cannot be usedfor precise analytic applications.

Anodic alumina (Whatman Anapore and Anotech Separation) offers a cheaperand morphologically better alternative to track-etch membranes, butinvolve handling dangerous reagent. In lab, reactive ion etching (RIE)can fabricate freestanding, perforated membranes with three complicatedsteps: vapor deposition, photolithography and RIE. In contrast, softlithography provides a simple way that involves spin-coating a thinlayer of liquid prepolymer on a substrate that contains microposts.However, the surface tension of the liquid prepolymer around themicroposts leads to uneven surface of the membrane.

It would therefore be advantageous to provide a method of fabrication offree standing open pore membranes having a low CV and capable ofproviding good quality pores with straight parallel walls through thethickness of the membrane as well as pore diameters that are the sameacross the membrane. It would also be very useful to provide a method ofproducing porous membranes in which the pore shape and morphology can becarefully controlled and tuned in order to provide shape selectiveporous membranes.

SUMMARY

Herein is disclosed a one-step photolithographic method of producingfree standing self-detached ultrathin membranes with open-pores array ofwell-defined patterns using only conventional photolithography. Bycontrolling the UV dose (intensity) and time of exposure of thephotoresist layer, free standing membranes can be produced within thephotoresist layer in which the exposed portion of the photoresist arenot adhered to the substrate on which the photoresist is deposited. Thecrosslinked part of photoresist forms the body of the membrane withwell-defined patterns reflective of the mask being used, while theuncrosslinked part of the photoresist layer adjacent to the substratesurface remains soluble during the process of photoresist development.This mechanism makes membranes easy to detach from substrates. Since theUV dose is controlled, the membrane thickness can be tuned by adjustingthe depth where crosslinking occurs in photoresist. This method can beapplied to any photosensitive material of choice, which may be selectedbased a need for certain desired material properties such ashydrophobicity, elasticity and ability for surface functionalization.

These membranes with uniform pore size and shape, and ordered poredistribution are ideal because of its superior performance toconventional membranes in many applications such as filtration, templatesynthesis and catalytic reaction. Such membranes have not yet been madeby existing membrane fabrication methods. Membranes made using thepresent method exhibit a coefficient of variation (CV) of pore size ofonly 0.15% compared to a CV value in a range of 15%-20% for conventionalmembranes. Using this method it is possible to produce membranes withspecially tailored sizes and shapes of pores on various substrates.Importantly, due to the self-detaching mechanism, the membranes areflat, and free of residual stress and deformation.

With accurate control of pore shape, such membranes enable filtration byshape compared to filtration by size only for majority of membranes. Insummary, this simple photolithographic method opens a new avenue tofabricate high-performance membranes that enables broad applications infiltration, separation, sorting and even new means of filtration likefiltration by shape.

Embodiments are disclosed which provide a method of fabrication of freestanding open pore membranes with uniform pore size and shape andordered pore distribution, and its use for synthesis of nanoparticlepatterns.

There is provided a method of fabrication of free standing polymericmembranes using negative photoresist, comprising the steps of:

a) providing a substrate having a top surface and applying a negativephotoresist layer to the top surface of the substrate;

b) heating the photoresist layer for a period of time;

c) exposing the photoresist layer from a top surface thereof to a doseof ultraviolet radiation through a mask having a predetermined pattern,controlling an intensity of the dose of ultraviolet radiation andcontrolling a time the photoresist layer is exposed to the dose ofradiation such that a top portion of the photoresist layer through whichthe dose of ultraviolet radiation enters the photoresist layer undergoesgreater cross linking than a bottom portion of the photoresist layerimmediately adjacent to the top surface of the substrate such that across linking gradient develops through a thickness of the photoresistlayer;

d) removing the mask,

e) heating the photoresist layer for another period of time again; and

f) dipping the substrate and photoresist into a developer solution, anddetaching the membrane from the top surface of the substrate to form afree standing patterned membrane having a preselected pattern of openpores reflective of the pattern of the mask.

There is also provided a method of fabrication of free standingpolymeric membranes using a positive photoresist, comprising the stepsof:

a) providing a transparent substrate having a top surface and applying apositive photoresist layer to the top surface of the substrate;

b) heating the photoresist layer for a period of time;

c) exposing the photoresist layer from its top to a dose of ultravioletradiation through a mask having a predetermined pattern such thatexposure causes scission of polymer chains in portions of thephotoresist layer exposed to the dose of ultraviolet radiation;

d) exposing the photoresist layer from its bottom to a dose ofultraviolet radiation without using any photomask, the dose ofultraviolet radiation being controlled in intensity and time thephotoresist layer is exposed such that scission of the polymer chainsonly occurs at a bottom portion of the photoresist layer through whichthe dose of ultraviolet radiation enters the photoresist layer (as aresult, the bottom portion of the photoresist layer becomes solubleduring the subsequent development;

e) removing the mask, and

f) dipping the substrate and photoresist into a developer solution, anddetaching the membrane from the top surface of the substrate to form afree standing patterned membrane having a preselected pattern of openpores.

The present invention also provides a method of fabrication of acomposite material comprised of nanoparticles (NPs) and the freestanding porous membranes by using the membranes as templates to confinethe movement of the nanoparticles, wherein the free standing membranesare exposed to the nanoparticles wherein said nanoparticles are confinedby the pores of the free standing membrane.

The pores have pre-selected size and shape to provide a shape selectivefilter.

A further understanding of the functional and advantageous aspects ofthe invention can be realized by reference to the following detaileddescription and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred embodiments will now be described, by way of example only,with reference to the drawings, in which:

FIG. 1 is a schematic representation of a gradient of the cross linkingprocess of a photoresist under UV exposure forming part of the presentprocess.

FIG. 2 is a schematic representation of a method of membrane fabricationusing negative photoresist according to the present invention.

FIGS. 3 a to 3 f show optical microscope images of membranes withdifferent sizes and shapes of pores made on various substrates: FIG. 3 ashows a membrane with small circular pores made on the Si wafer; FIG. 3b shows a membrane with large circular pores made on the normal flatglass; FIG. 3 c shows a membrane with hexagonal pores made on thepolyethylene terephthalate (PET) film; FIGS. 3 d, 3 e, 3 f showsmembranes with elliptical pores, triangular pores and the letters “UWO”made on the glass slides of microscope.

FIGS. 4 a to 4 d show optical microscope images of membranes: FIG. 4 bshows a photographic image of a piece of a membrane with thickness lessthan 20 pm unfolding evenly; FIG. 4 b shows an SEM image demonstratingthe flexibility and the micro scale flatness of membrane in which theflatness is further displayed by a zoom in view, showing that the areaof trenches transits smoothly to the pores; FIG. 4 c shows the profileof pores in membranes shows pores were distributed evenly among thecrosslinked photoresist, and the inner walls of those pores are smooth;FIG. 4 d shows the size of the pores do not change appreciably from thetop to the bottom through the thickness of the membrane.

FIG. 5 shows topography representations and section analysis of AFMmeasurements of membranes: FIG. 5 a shows the scan area of the largeimage is 3×3 μm² while the scan area of the inset is 30×30 μm², thewhite open square in the inset indicates the area scanned for the largeimage; FIG. 5 b shows the height profile across the dotted line showsthat the roughness is within ±10 nm.

FIG. 6 shows statistical results of self-detached membranes in whichFIG. 6 a is a plot showing membrane thickness versus exposure timeduring the cross linking step and shows the thickness of the detachedmembranes gradually decreased when the exposure time was reduced; FIG. 6b shows the thinner the membrane (lesser exposure dose), the greater thedeviation of pore size came from the designed pore size of thephotomask.

FIG. 7 is a schematic representation of a method of membrane fabricationusing positive photoresist according to the present invention.

FIG. 8 is an image taken by blackfield optical microscope showing Agnanparticle ring arrays patterned with freestanding membranes.

FIG. 9 is an optical image taken by blackfield optical microscopeshowing Ag nanoparticles in a disc array patterned with freestandingmembranes.

DETAILED DESCRIPTION

Generally speaking, the embodiments described herein are directed to amethod of fabrication of free standing membranes and synthesis ofnanoparticle patterns using the free standing porous membranes. Asrequired, embodiments of the present invention are disclosed herein.However, the disclosed embodiments are merely exemplary, and it shouldbe understood that the invention may be embodied in many various andalternative forms.

The figures are not to scale and some features may be exaggerated orminimized to show details of particular elements while related elementsmay have been eliminated to prevent obscuring novel aspects. Therefore,specific structural and functional details disclosed herein are not tobe interpreted as limiting but merely as a basis for the claims and as arepresentative basis for teaching one skilled in the art to variouslyemploy the present invention. For purposes of teaching and notlimitation, a method of fabrication of free standing membranes andsynthesis of nanoparticle patterns is disclosed herein.

As used herein, the terms “about”, and “approximately” when used inconjunction with ranges of dimensions, concentrations, temperatures orother physical or chemical properties or characteristics is meant tocover slight variations that may exist in the upper and lower limits ofthe ranges of properties/characteristics.

As used herein, the phrase “negative photoresist” refers to a polymerphotoresist material which, under exposure to UV light causes thenegative resist to become polymerized, and more difficult to dissolve.Therefore, the exposed part of the negative resist remains on thesurface of the substrate it is located on where it is exposed, and adeveloper solution is used to remove only the unexposed portions.

As used herein, the phrase “postive photoresist” refers to a polymerphotoresist material that behaves in the opposite manner to a negativephotoresist, such that, exposure to UV light changes the chemicalstructure of the resist so that it becomes more soluble in thedeveloper. The exposed resist is then washed away by the developersolution.

As used herein, the phrase “scission” means breaking down of the polymerchains under UV exposure.

The present invention provides a novel and easy to control fabricationtechnique for preparing self-detachable, open-pore membranes synthesizedfrom photocurable resist using a one-step photolithography process.

The present method uses precise control of exposure dose on thephotoresist, which induces the membranes to detach from the substrate.When a negative photoresist is used, as illustrated in FIG. 1, as the UVlight shines through the photoresist perpendicularly from the topsurface to the bottom surface, the top part of the sample absorbs UVenergy and cross links in prior to the bottom surface. Only if theimpinging UV energy is enough, the catalyzer of the photopolimerizationdiffuses to the bottom region, inducing cross linking of the completedsample. This gradient cross linking mechanism can be utilized tofabricate the self-detached and patterned membrane. The UV dose forsample was controlled so that the bottom region without cross linkingwas dissolved in the chemical developing process, while the crosslinking top region was cured and detached from the substrate. Themembrane thickness depends on the ratio of cross linking photoresist andun-cross linking photoresist, in other word, the amount of UV dose.

To emphasise, the factor key to obtaining the self-detachment of themembrane is to produce a gradient of UV exposure in the photoresist. Intraditional photolithography, a specific amount of UV dose is requiredin order to make completed crosslink throughout the photoresist layer.However, in this so-called moderate photolithographic method, the amountof UV dose is less than the standard UV dose, for the particular purposeof generating a gradient of UV dose received inside the photoresist. Asa result, a gradient degree of crosslinking is formed in the verticaldirection of the photoresist.

Referring to FIGS. 1 and 2, as the UV light shines perpendicularly intoa layer of the negative photoresist from its top surface to its bottomsurface through a mask (having a desired pattern for producing acorresponding pattern of pores in the final membrane), the top part ofthe photoresist absorbs the required amount of UV energy to generateenough protonic acid to crosslink the top part of the photoresist. Thecured surface layer becomes thicker as the photosensitizer concentrationincreases, thereby blocking more UV light being transmitted downwardtoward the bottom surface adjacent to the top surface of the substrate.Only when the incident UV dose is high enough, the catalyzer of thephotopolymerization diffuses to the bottom region, inducing crosslinkingof the entire layer of the photoresist. Therefore, a photoresist layerwith a gradient degree of crosslinking is formed as shown in FIG. 1.

The bottom region of the photoresist remained uncrosslinked, and thus itcould be dissolved by the developer solution. On the contrary, thecrosslinked top region forms the body of the membrane and is detachedfrom the substrate to produce the free standing porous membrane. Usingthis method, high density pore arrays can be fabricated as easily as thelow density ones as long as photolithography technique allows.

The present invention will now be illustrated with the followingnon-limiting but exemplary examples.

EXAMPLE 1

In a first example, SU-8, a negative photoresist, was used to producethe membranes and photolithography through a mask was used to define themicropatterns. SU-8 is a negative photoresist type epoxy, is widely usedin the microfabrication of biological devices because of itshydrophobicity and biocompatibility.

The fabrication process is as follows. Silicon wafers were firstcarefully cleaned in the heated piranha solution, rinsed in DI water anddried on a hotplate (200° C.) for 5 min. The negative photoresist (SU-83010, Microchem, USA) was spun at 500 rpm for 5 sec followed by 1000 rpmfor 30 sec on the clean Si wafer using a spin coater (Solitec 5110Spinner). 5 min soft baking at 95° C. was needed to remove the excesssolvent from the SU-8 layer. Then the SU-8 layer was exposed to UV lightthrough a photomask using a mask aligner (Karl SussMA6 Mask Aligner,sensor wavelength=365 nm, UV intensity 6 mw cm⁻²). After thepost-exposure bake at 65° C. for 1 min and 95° C. for 3 min, the SU-8layer was developed using the SU-8 developer with manual agitation.Ultrasonic agitation can help and speed up the process of development bydisrupting the dissolved SU-8 at the edges to allow chemical contactbetween the developer and the SU-8 at the centre. Gradually, thepatterned membranes were detached from the wafer and floated in thesolution. It took another 30 sec to fully dissolve the uncrosslinkedphotoresist around the pores, and then the membrane was taken out fromthe developer and rinsed with isopropanol followed by deionised water.Finally, the membranes were laid on flat surfaces and covered with glassslides. to prevent the membranes from curving during the dehydrationstep.

The pore size of membranes can be accurately controlled using thismethod. The membrane in FIG. 3 a demonstrates a porosity of 1.2×10⁵pores cm⁻² and its mean pore diameter (M) is 20 μm with a standarddeviation (σ) of 30 nm. The coefficient of variation (CV=σ/M) is only0.15%. This is a major advantage in comparison with track-etchedmembranes that show a CV of 15%-20%, and even better thanmicrofiltration membranes (7%) built with aperture array lithography.Accuracy is ensured by two mechanisms. Firstly, the photolithographytechnique can pattern microstructures in accordance with the patterns onphotomasks. Secondly, the self-detached mechanism guarantees that thepatterned pores are not deformed when the membranes are separated fromtheir substrates. The accuracy of pore size dominates the retention R,which is one of the vita parameters characterizing membrane selectivity.The retention can be determined by comparing the concentration ofsubstance i retained s_(i,r) and feeded s_(i,f). The retention R, isdefined as s_(i.r)/s_(if), so it can be altered from 0, which means noretention of substance i, to 1, which indicates substance i iscompletely retained. The ratio of substance size to pore size providesthe major contribution to this variation. Therefore, the retention ofour membranes can be adjusted by precisely adjusting the pore size,which greatly increases the controllability of retention.

The useful features of this method are not only the accurately definedpore sizes, but also the uniformly distributed pores. The percentage ofoverlapped pores of the present membranes was controlled as about 0%,which is a very significant improvement over most of the existingcommercial porous membranes. Furthermore, such uniformity remains notonly within one piece of membrane, but also for different batches ofmembranes. The excellent uniformity and reproducibility are due to thestability of photolithography, and are further consolidated by theself-detachment mechanism disclosed herein. Besides the accuracy of poresize and uniformity of pores distribution, the pore shape can bewell-defined as well, which may yield novel barrier structure, and thusfurther enhance the robustness of retention.

This porous barrier could be used in the precise permselectiveseparations for substances that have subtle difference in size, butobvious difference in shape. Suppose that a kind of round shapedsubstance were extracted from another kind of hexagonal substance withthe same size. This is not possible using size-based membranes, but thepresent shape-based membranes provide an executive solution. This opensthe possibility of developing a new mode of filtration based not only onthe sizes of substances, but also on their shapes. Circular, hexagonal,elliptical, triangular pores and even letters were fabricated anddemonstrated to verify the robustness of this method as shown in FIGS. 3a to 3 f.

Another useful feature of this method is the regularity of membranes.From the surfaces to the internal walls of pores, the whole piece ofmembrane was perfectly fabricated without any discernible defects. Asshown in FIG. 4 a, a piece of membrane with a thickness of 20 μm caneasily remain flat and smooth.

If such a thin membrans were detached from a mold or a substrate byexotic methods, it would very likely be distorted or even damaged by theexternal force or the residual stress. However, as shown in FIG. 4 b,the self-detached membrane remains intact. The smoothness of themembrane surface was further quantified at nanoscale using atomic forcemicroscopy (AFM). The topography of SU-8 membranes is shown in FIG. 5 aand a height profile is provided as its section analysis in FIG. 5 b.Characterized from AFM data, the roughness of membranes was just within±10 nm. The regularity is also displayed by the the profile of pores.FIG. 4 c shows that the pores are distributed evenly in the membrane andthe inner walls of those pores are smooth. The axes of pores wereparallel to the normal of membrane surface. From an enlarged view of theinner wall (FIG. 4 d), we can see that the diameter and shape of thepores remain nearly unchanged throughout the pores in the depthdirection. These merits of membranes can reduce the possibility of theformation of a particle aggregation across the pore constriction whenparticles, smaller in size than the pore, simultaneously pass throughthe pore. This leads to the high flux in the application of filtration.These robust membranes can be built on a variety of substrates. Forexample, the membranes in FIGS. 3 a to 3 f were fabricated on siliconwafers, regular flat glasses, polyethylene terephthalate (PET) films andmicroscope glass slides, respectively. The only difference among them isthe flatness. As the flatness of the silicon wafer is greater than theother three, the membrane made on silicon wafer was flatter than theothers, which is why the appearance of the membranes in FIG. 3 a lookssmoother and cleaner.

Control of thickness is a crucial factor in the creation of membranes.The thickness of self-detached membranes is proportional to the exposuredose of UV in this method. With a regular exposure time (t_(e), 33 sec)for SU-8 3010 spun at 1000 rpm, a SU-8 layer of 21±0.3 μm can completelycrosslink and adhere to its substrate. On the contrary, if the exposuredose were too low, the whole SU-8 layer would be totally dissolved inthe developer. The self-detaching phenomenon occurred in the developmentstep for t_(e) shorter than 33 sec. FIG. 6 a shows the relation of t_(e)to the thicknesses of SU-8 membranes, which are measured by the DektakSurface Profilometer. As the exposure time reduced, the thickness of theself-detached membranes gradually decreased. Therefore, one can inferthat membranes with other thickness can be fabricated by adjusting thespinning speed for photoresist SU-8 or using other kinds of photoresistand applying different UV exposure dosage.

Since a lower UV dose was applied compared to the required UV dose forthe traditional photolithography process, photoresist at the edges ofpores might not crosslink completely, which may lead to partialdissolution when reacting with the developer. As a result, the pore sizeof membranes might become slightly larger than that of the photomask. Itis delightful that such discrepancy is tiny and fits in a predictabletrend. Based on experimental data, the relationship between membranethickness and pore size is statistically shown in FIG. 6 b. As seen fromthe data, the thinner the membranes were, the greater the deviation ofactual pore size from the designed value. Knowing the correlationbetween membrane thickness and the relevant deviation of pore size, wecan achieve the desired pore size by compensating the difference, i.e.,by slightly reducing the pore size on the photomask.

EXAMPLE 2

FIG. 7 shows the process of fabrication of membranes with positivephotoresist in which most of the steps are similar to the process ofusing negative photoresist except the exposure step. The photoresistlayer is exposed from its top to a dose of ultraviolet radiation througha mask having a predetermined pattern, exposure causes scission of thepolymer chains at the top parts of the photoresist layer. Then thisphotoresist layer is exposed from its bottom to a dose of ultravioletradiation without any photomask, the dose of ultraviolet radiation beingcontrolled in intensity and time the photoresist layer is exposed suchthat scission of the polymer chains only occurs at a bottom portion ofthe photoresist layer through which the dose of ultraviolet radiationenters the photoresist layer.

Thus in this embodiment using a positive photoresist based polymer, themethod of fabrication of free standing polymeric membranes comprisingthe steps of: a) providing a transparent substrate having a top surfaceand applying a positive photoresist layer to the top surface of thesubstrate; b) heating the photoresist layer for a period of time; c)exposing the photoresist layer from its top to a dose of ultravioletradiation through a mask having a predetermined pattern such thatexposure causes scission of polymer chains in portions of thephotoresist layer exposed to the dose of ultraviolet radiation; d)exposing the photoresist layer from its bottom to a dose of ultravioletradiation without any photomask, the dose of ultraviolet radiation beingcontrolled in intensity and time the photoresist layer is exposed suchthat scission of the polymer chains only occurs at a bottom portion ofthe photoresist layer through which the dose of ultraviolet radiationenters the photoresist layer (as a result, the bottom portion of thephotoresist layer becomes soluble during the subsequent development); e)removing the mask, and f) dipping the substrate and photoresist into adeveloper solution, and detaching the membrane from the top surface ofthe substrate to form a free standing patterned membrane having apreselected pattern of open pores.

EXAMPLE 3

Working as templates to confine the movement of nanoparticles (NPs),These membranes can be employed to pattern NPs array. Based on coffeering effect, the particles in a droplet prefer flowing toward theperimeter under capillary forces, and that results in higherconcentration of particles at the perimeter than other area in thedroplet. Membranes were employed here to further define the boundary ofNPs movement. They were attached on a flat surface, and NPs weredistributed among those pores array by spraying. After evaporation, theNPs were patterned, and the membranes can be easily peeled off, leavingthe NPs array. By changing the concentration of NPs solution used inspraying, NPs rings (FIG. 8) and NPs discs (FIG. 9) were built upuniformly with high repeatability. Various kinds of NPs patterns can bebuilt up through membranes with different pore shapes.

The method is not limited to the materials referred to in the Examples.For example, the negative photoresist may be, but is not limited to, theSU-8 3000 Series, the SU-8 2000 Series, and the KMPR 1000 Series tomention just a few. The substrate may be any solid includingsemiconductors such as but not limited to silicon wafers. It may be anypolymer material, glasses, metals, glass slides, vinyl sheets, mica,graphite and any plastic to mention just a few. The developer solutionmay be 1-Methoxy-2-propyl acetate, or TMAH aqueous alkaline developer tomention just a few. Besides spraying, any other method of applying thenanoparticles may be used including dip coating, spin coating andplating methodologies to mention a few non-limiting techniques.

The present method is very advantageous compared to existing commercialproducts or laboratory methods, in that the present method can be usedto fabricate self-detached membranes with complicated patterns andvarying thicknesses in a one step process. The present method does notinvolve handling any dangerous reagent. Due to the self-detachedmechanism, the membranes made with this method are free of residualstress and deformation. This fabrication method is less expensive, butsuitable for large-scale production. With these freestanding membranes,various NPs array are easily patterned by spraying.

In disclosed herein is a simple yet robust method to fabricateself-detached membranes of SU-8 with well-defined pore size, shape anddistribution and with controllable thickness based on conventionalphotolithography. The essence of this method is that a gradient degreeof crosslinking is formed in the photosensitive material, which resultsin self-detached membranes. Free standing membranes with speciallytailored sizes and shapes of pores have been prepared on varioussubstrates. Advantageously, due to the self-detaching mechanism, themembranes produced by this method are flat, and free of residual stressand deformation. Another important advantage is that accurate control ofpore shape, such membranes enable filtration by shape compared tofiltration by size for a majority of membranes. In summary, this simplephotolithographic method opens a new avenue to fabricatehigh-performance membranes that enables broad applications infiltration, separation, sorting and even new means of filtration likefiltration by shape.

As used herein, the terms “comprises”, “comprising”, “includes” and“including” are to be construed as being inclusive and open ended, andnot exclusive. Specifically, when used in this specification includingclaims, the terms “comprises”, “comprising”, “includes” and “including”and variations thereof mean the specified features, steps or componentsare included. These terms are not to be interpreted to exclude thepresence of other features, steps or components.

The foregoing description of the preferred embodiments of the inventionhas been presented to illustrate the principles of the invention and notto limit the invention to the particular embodiment illustrated. It isintended that the scope of the invention be defined by all of theembodiments encompassed within the following claims and theirequivalents.

1. A method of fabrication of free standing polymeric membranes usingnegative photoresist, comprising the steps of: a) providing a substratehaving a top surface and applying a negative photoresist layer to thetop surface of the substrate; b) heating the photoresist layer for aperiod of time; c) exposing the photoresist layer from a top surfacethereof to a dose of ultraviolet radiation through a mask having apredetermined pattern, controlling an intensity of the dose ofultraviolet radiation and controlling a time the photoresist layer isexposed to the dose of radiation such that a top portion of thephotoresist layer through which the dose of ultraviolet radiation entersthe photoresist layer undergoes greater cross linking than a bottomportion of the photoresist layer immediately adjacent to the top surfaceof the substrate such that a cross linking gradient develops through athickness of the photoresist layer; d) removing the mask, e) heating thephotoresist layer for another period of time again; and f) dipping thesubstrate and photoresist into a developer solution, and detaching themembrane from the top surface of the substrate to form a free standingpatterned membrane having a preselected pattern of open pores reflectiveof the pattern of the mask.
 2. The method according to claim 1 whereinsaid negative photoresist is selected from the group consisting of SU-83000 Series, SU-8 2000 Series, KMPR 1000 Series.
 3. The method accordingto claim 1 wherein said substrate is selected from the group consistingof silicon wafers, glass slides, vinyl sheets, metal plates, mica,graphite and any plastic.
 4. The method according to claim 1 whereinsaid developer solution is selected from the group consisting1-Methoxy-2-propyl acetate, and TMAH aqueous alkaline developer.
 5. Amethod of fabrication of a composite material comprised of nanoparticles(NPs) and the free standing porous membranes recited in claim 1 by usingsaid membranes as templates to confine the movement of thenanoparticles, wherein said free standing membranes are exposed to thenanoparticles wherein said nanoparticles are confined by the pores ofthe free standing membrane.
 6. The method of claim 5 wherein saidnanoparticles are applied to said free standing membrane by any one orcombination of spraying, dip coating, spin coating and plating.
 7. Afree standing membrane with said preselected pattern of open poresproduced by the method of claim
 1. 8. The free standing membrane ofclaim 7 wherein said pores have pre-selected size and shape to provide ashape selective filter.
 9. A method of fabrication of free standingpolymeric membranes using a positive photoresist, comprising the stepsof: a) providing a transparent substrate having a top surface andapplying a positive photoresist layer to the top surface of thesubstrate; b) heating the photoresist layer for a period of time; c)exposing the photoresist layer from its top to a dose of ultravioletradiation through a mask having a predetermined pattern such thatexposure causes scission of polymer chains in portions of thephotoresist layer exposed to the dose of ultraviolet radiation; d)exposing the photoresist layer from its bottom to a dose of ultravioletradiation without any photomask, the dose of ultraviolet radiation beingcontrolled in intensity and time the photoresist layer is exposed suchthat scission of the polymer chains only occurs at a bottom portion ofthe photoresist layer through which the dose of ultraviolet radiationenters the photoresist layer; e) removing the mask, and f) dipping thesubstrate and photoresist into a developer solution, and detaching themembrane from the top surface of the substrate to form a free standingpatterned membrane having a preselected pattern of open pores.
 10. Themethod according to claim 9 wherein said positive photoresist isselected from the group consisting of Polymethyl methacrylate (PMMA),Microposit 1800 Series, AZ Series.
 11. The method according to claim 9wherein said transparent substrate is selected from the group consistingof glass slides, glass wafers, vinyl sheets, PET (polyethyleneterephthalate) sheets, and transparent plastic sheets.
 12. The methodaccording to claim 9 wherein said developer solution is selected fromthe group consisting of Methyl Isobutyl Ketone (MIBK) and isoproponaland Microposit MF 319 Developer.
 13. A method of fabrication of acomposite material comprised of nanoparticles (NPs) and the freestanding porous membranes recited in claim 7 by using said membranes astemplates to confine the movement of the nanoparticles, wherein saidfree standing membranes are exposed to the nanoparticles wherein saidnanoparticles are confined by the pores of the free standing membrane.14. The method of claim 13 wherein said nanoparticles are applied tosaid free standing membrane by any one or combination of spraying, dipcoating, spin coating and plating.
 15. A free standing membrane withsaid preselected pattern of open pores produced by the method of claim9.
 16. The free standing membrane of claim 15 wherein said pores havepre-selected size and shape to provide a shape selective filter.
 17. Themethod according to claim 2 wherein said substrate is selected from thegroup consisting of silicon wafers, glass slides, vinyl sheets, metalplates, mica, graphite and any plastic.
 18. The method according toclaim 2 wherein said developer solution is selected from the groupconsisting 1-Methoxy-2-propyl acetate, and TMAH aqueous alkalinedeveloper.
 19. A method of fabrication of a composite material comprisedof nanoparticles (NPs) and the free standing porous membranes recited inclaim 2 by using said membranes as templates to confine the movement ofthe nanoparticles, wherein said free standing membranes are exposed tothe nanoparticles wherein said nanoparticles are confined by the poresof the free standing membrane.
 20. The method of claim 19 wherein saidnanoparticles are applied to said free standing membrane by any one orcombination of spraying, dip coating, spin coating and plating.